[0001] This invention relates to a sodium sulfur cell for use in a weightless environment.
[0002] Rechargeable cells or batteries are electrochemical devices for storing and retaining
an electrical charge and later delivering that charge for useful power. Familiar examples
of the rechargeable cell are the lead-acid cell used in automobiles and the nickel-cadmium
cell used in portable electronic devices such as cameras. Another type of cell having
a greater storage capacity for its weight is the nickel oxide pressurized hydrogen
cell, an important type of which is commonly called the nickel-hydrogen cell and is
used in spacecraft applications.
[0003] Yet another type of cell is the sodium sulfur cell, which has been under development
for about 20 years for use in a variety of terrestrial applications such as nonpolluting
electric vehicles. The sodium sulfur cell has the particular advantage that its storage
capacity per unit weight of cell is nearly three times, and in some designs as much
as five times, the storage capacity of the nickel-hydrogen cell. The sodium sulfur
cell therefore is an attractive candidate for use in spacecraft applications.
[0004] The most common type of construction for a sodium sulfur cell includes a cylindrical
metal outer housing which serves as a positive terminal and a cylindrical shell of
an alumina based ceramic within the outer housing. Sodium is placed into a first or
inner chamber formed within the alumina shell, and sulfur is placed into a second
chamber formed between the alumina shell and the outer housing. The cell is heated
to a temperature of about 350 C, at which temperature both the sodium and the sulfur
are molten. The liquid sodium acts as the anode of the cell, the liquid sulfur acts
as the cathode, and the solid ceramic acts as the electrolyte. Electrical energy is
released when sodium ions diffuse through the ceramic into the sulfur, thereby forming
sodium polysulfides. Electrical energy can be stored when the process is reversed,
with an applied voltage causing the sodium polysulfides to decompose to yield sodium
and sulfur, and the sodium ions diffuse through the ceramic electrolyte back into
the first chamber.
[0005] The sodium sulfur cell is under consideration for many applications requiring a high
capacity of electrical energy storage, such as electrically powered automobiles. It
has not as yet found widespread use because of the state of development of such electrically
powered vehicles, and because of engineering problems associated with the operation
of the cell at elevated temperatures, in the automotive environment.
[0006] The sodium sulfur cell is also a candidate for use in energy storage for spacecraft
such as communications satellites. A satellite orbiting the earth is exposed to intense
sunlight and then plunged into shadow in a periodic manner. In most satellites, electrical
energy to power the systems on board the satellite is created by solar cells that
function when the satellite is in sunlight, and a portion of the electrical energy
so generated is stored in electrical storage cells. The stored energy is then available
for use when the satellite is in the earth's shadow or for peak power demands, by
discharging the cells.
[0007] Nickel-cadmium and nickel-hydrogen electrical storage cells are currently used in
many satellite applications. Such cells have the capacity to store at most about 37.5
- 39.5 watt hours per kg (17 - 18 watt hours per pound) of battery weight. A sodium
sulfur cell has the capacity to store over 110.5 watt hours per kg (50 watt hours
per pound) of battery weight using existing cell designs. In one example, about 304
kg (670 pounds) of nickel-hyrogen cells are required in a communication satellite
to meet its storage needs. If the nickel-hydrogen cells were replaced by sodium sulfur
cells, the weight of storage cells would be reduced to less than 113.4 kg (250 pounds).
The weight of the cells is included in the cost of launching the satellite, which
presently is in the order of US $ 44,092 per kg (US $ 20,000 per pound), and a potential
reduction of over 181.4 kg (400 pounds) is highly significant.
[0008] EP-A-376 059 discloses a sodium sulfur cell of the common type of construction mentioned
above. The sulfur is put under pressure, in order to prevent the sodium from flowing
to the cathode space in case the solid electrolyte is damaged. A chemical compound,
namely sodium azide, is provided which decomposes at the operating temperature of
the cell into an inert gas and another compound. This document is prior art according
to Art. 54(3),(4) EPC.
[0009] A further sodium sulfur cell is disclosed in FR-A-2 315 777. The sodium chamber of
this cell is arranged at the cell periphery, and the sulfur chamber is inside of the
sodium chamber. A central space is filled with an inert gas (e.g. argon). When the
cell is discharged, the polysulfides expand into the inner space, against gas pressure.
The increased gas pressure than helps to remove the polysulfides if the cell is charged
again.
[0010] Although sodium sulfur cells offer potential benefits in spacecraft applications,
their operation has been established only on earth. A key difference between operation
in a terrestrial environment and in a spacecraft is the absence of gravity in space.
It has been determined that the absence of gravity may have significant adverse effects
on the functioning of the cell, particularly under fast discharge conditions, that
are not experienced in earthbound applications. There is a need to develop an approach
to avoiding the expected adverse effects prior to building and launching such cells.
[0011] It is therefore an object of the present invention to provide a process for releasing
previously stored electrical energy in a weightless environment using a sodium sulfur
electrical storage cell of the kind mentioned above.
This object is achieved by a process including the steps of:
- furnishing a sodium sulfur electrical storage cell including a sodium anode, a sulfur
cathode, a solid ceramic electrolyte separating the sodium anode and the sulfur cathode,
and pressure means for applying a pressure to said sulfur cathode;
- heating the sodium sulfur electrical storage cell to a temperature of at least about
300° Celsius in a weightless environment;
- permitting sodium cations to diffuse from the sodium anode to the sulfur cathode through
the solid ceramic electrolyte, wherein
- said pressure means applies a pressure to said sulfur cathode which is greater than
the vapor pressure of the sulfur at the operating temperature of the cell, in order
prevent the formation of bubbles in the sulfur.
[0012] The present invention provides thus a process for storing and obtaining previously
stored energy, that avoids one of the problems associated with use of such cells in
a weightless environment. The approach of the invention does not significantly alter
the basic structure and operation of the cell, but does avoid a high cell impedance
and associated limitations on rate of discharge when the cell is operated in the absence
of gravity. The preferred approach adds little to the cost and weight of the cell.
[0013] In accordance with the invention, a sodium sulfur electrical storage cell comprises
a sodium anode; a sulfur cathode; a solid ceramic electrolyte separating the sodium
anode and the sulfur cathode; and means for pressurizing the sulfur cathode to prevent
the formation of bubbles in the sulfur.
[0014] At the operating temperature of about 350 C, the sodium anode and the sulfur cathode
in a sodium sulfur cell are molten. It is possible that bubbles may form within these
phases, and in particular the formation of bubbles in the sulfur phase can result
in a progressive increase in the internal impedance of the cell and its eventual failure
in the sense of being unable to store further electrical charge, for the reasons to
be discussed next.
[0015] As the sodium sulfur cell discharges, the sodium cations diffuse through the ceramic
electrolyte separating the anode and the cathode, toward the sulfur cathode. When
the sodium cations have passed entirely through the ceramic electrolyte, they meet
the sulfur anions and combine to form sodium polysulfides. The formation of the sodium
polysulfides is highly exothermic, so that the region of the sulfur cathode immediately
adjacent to the surface of the ceramic electrolyte is heated above the general operating
temperature of the cell.
[0016] Gas bubbles may form in the sulfur simultaneously and independently of the polysulfide
reaction. The gas bubbles contain vaporized sulfur and/or other gases that were sealed
into the cell when it was manufactured. In cells used on earth, the bubbles tend to
float upwardly, because they are less dense than the surrounding liquid sulfur, and
collect at the top end of the cell where they are harmless. In a weightless environment,
there is no gravity to drive the bubbles upward.
[0017] Instead, the bubbles in the sulfur tend to migrate toward the hottest parts of the
system and remain there, another manifestation of the Maringoni effect that has been
previously observed in liquid spacecraft propellant tanks. As discussed above, the
locally hottest part of the sulfur cathode is immediately adjacent to the ceramic
electrolyte, and the bubbles tend to migrate to this region. Since there are no convection
currents in a weightless environment, once the bubbles have reached this region, they
will stay there.
[0018] The gradual accumulation of bubbles adjacent to the electrolyte impedes the reaction
of the sodium cations and the sulfur anions to form sodium polysulfides, by preventing
sulfur ions from reaching this region. The externally observed result is a gradual
decrease in the capacity of the cell and an increase in its internal impedance.
[0019] The present invention provides means for avoiding the presence of bubbles within
the sulfur. The adverse effects of bubbles may be avoided by various approaches, including
prevention of their formation and avoiding the adverse effects, once the bubbles have
formed. The preferred approach is to entirely avoid the formation of the bubbles,
because removal of bubbles after formation is difficult in view of the electrically
conductive inner structure of the cathode, to be discussed in more detail later. One
method of practicing the preferred approach is to apply a gas pressure to the sulfur
cathode of sufficiently high pressure to suppress formation of the bubbles in the
sulfur. Such pressure should be at least as great as the vapor pressure of the sulfur
at the operating temperature of the cell, as this pressure is sufficient to prevent
the sulfur from vaporizing.
[0020] A positive pressure can be applied to the sulfur in several ways. One such approach
is the application of pressure from an external pressurization source. The normal
procedure of cell fabrication includes sealing the cell completely so that neither
the sulfur nor the sodium can escape, and providing an external pressurization source
could also provide an escape path for these components. It is therefore preferable
to apply the pressure to the sulfur with the cell sealed.
[0021] The most preferred approach to applying the pressure to the sulfur cathode is to
include within the chamber containing the sulfur a source of a gas that does not dissolve
appreciably in the sulfur. The source is provided at a location remote from the surface
of the ceramic electrolyte, so that the gas forms a pocket that expands to apply a
pressure to the sulfur without being able to collect in the region near the electrolyte
surface. The preferred source of such gas is the solid sodium azide, NaN₃, which decomposes
to produce sodium and gaseous diatomic nitrogen molecules at the operating temperature
of the cell.
[0022] Thus, further in accordance with the invention, a sodium sulfur electrical storage
cell comprises a cell housing having a first chamber and a second chamber therein;
a sodium anode within the first chamber of the housing; a sulfur cathode within the
second chamber of the housing; a solid ceramic electrolyte separating the sodium anode
and a sulfur cathode; and a quantity of pressurizing gas within the second chamber
sufficient to pressurize the sulfur above its vapor pressure, the pressurizing gas
being substantially insoluble in the sulfur. The pressurizing gas is most preferably
provided by including in a location of the second chamber, remote from the electrolyte,
a quantity of a compound such as sodium azide that vaporizes to produce a pressurizing
gas and a metal or other element that does not adversely affect the operation of the
cell. Since sodium is already present in the cell, it is preferred as the metallic
decomposition product.
[0023] The present invention also extends to a process for storing and obtaining energy.
As related to the discharge of the cell, a process for releasing previously stored
electrical energy in a weightless environment comprises the steps of furnishing a
sodium sulfur electrical storage cell, the cell including a sodium anode, a sulfur
cathode, a solid ceramic electrolyte separating the sodium anode and the sulfur cathode,
and means for avoiding bubbles in the sulfur; heating the electrical storage cell
to a temperature of at least about 300C in a weightless environment; and permitting
sodium cations to diffuse from the sodium anode to the sulfur cathode, through the
solid ceramic electrolyte, while avoiding bubbles in the sulfur, thereby releasing
previously stored electrical energy. The same approach previously described applies
equally to this process.
[0024] It will be appreciated that the present invention provides an advance in the art
of sodium sulfur cells, which advance is critical to the application of such cells
in a weightless environment. By avoiding the accumulation of bubbles in the sulfur,
the gradual deterioration in cell performance associated with accumulation of bubbles
adjacent to the surface of the electrolyte is avoided. Other features and advantages
of the present invention will be apparent from the following more detailed description
of the preferred embodiment, taken in conjunction with the accompanying drawings,
which illustrate, by way of example, the principles of the invention.
Figure 1 is a side sectional drawing of a sodium sulfur cell of the invention;
Figure 2 is an enlarged pictorial representation of a detail of Figure 1, illustrating
a section through the region adjacent to the electrolyte;
Figure 3 is a pictorial representation corresponding to Figure 2, with the temperature
distribution during cell discharge graphically superimposed; and
Figure 4 is a pictorial representation of a sodium sulfur cell and pressurization
apparatus employing another embodiment of the invention.
[0025] A presently preferred form of a sodium sulfur cell 10 of the invention is illustrated
in Figure 1. The cell 10 includes an outer cylindrical housing 12 (also termed the
first cylindrical shell) in which the other components of the cell are contained.
To permit assembly, the housing 12 has a top portion 14 and a bottom portion 16, with
a seal 18 between them. After assembly, the housing 12 is hermetically sealed. Within
the housing 12 is a cylindrical protection tube 20 (also termed the second cylindrical
shell) dimensioned to fit within, and disposed to be coaxial with, the housing 12.
[0026] An electrolyte 22 is a solid ceramic in the form of a third cylindrical shell that
is coaxial with, and disposed between, the housing 12 and the protection tube 20.
The electrolyte 22 is a ceramic material that permits the rapid diffusion of sodium
ions therethrough. In its most preferred form, the ceramic electrolyte 22 is beta/beta
double prime alumina of a composition of about 90% aluminum oxide, 9% sodium oxide,
and 1 percent lithium oxide. (All compositions herein are in percent by weight, unless
otherwise indicated.) The present invention is not limited to any particular composition
of electrolyte, however.
[0027] Elemental sodium is contained within the protection tube 20. At one end of the protection
tube 20 is an orifice 25 through which the interior of protection tube 20 communicates
with the volume between the protection tube 20 and the electrolyte 22, termed the
first chamber 24. When molten, the sodium flows from within the protection tube 20,
through the orifice 25, and into the first chamber 24 by wicking or capillary action.
[0028] Elemental sulfur is contained within the volume between the housing 10 and the electrolyte
22, termed the second chamber 26. Additionally, this second chamber 26 is filled with
a porous graphite felt 28 (illustrated in Figure 2) made up of electrically conductive
graphite fibers. The packing density of graphite fibers in the felt 28 is such that
the sulfur, when molten, is free to flow through the felt 28. The felt 28 provides
electrical conductivity through the second chamber 26.
[0029] The region of the cell 10 adjacent to the electrolyte 22 is illustrated in more detail
in Figure 2. During operation, the cell 10 is heated to a temperature at which the
sulfur and the sodium are molten, preferably about 350 C. Molten sodium flows into
the first chamber 24. Sodium cations diffuse through the electrolyte 22 from the first
chamber 24 toward the second chamber 26. Upon reaching the second chamber 26, the
sodium cations combine with sulfur anions at, and immediately adjacent to, an outer
surface 30 of the electrolyte 22.
[0030] The sodium half-cell reactions for discharge are
2 Na = 2 Na⁺ + 2 e⁻
x S + 2 e⁻ = (S
x)⁻².
The total reaction of the cell is therefore
2 Na + x S = Na₂S
x.
The electrons flow through an external circuit during the reaction. The reaction is
presented in this manner because the sodium polysulfide Na₂S
x may be present in several forms, depending upon the degree of discharge of the cell
10. With increasing degrees of discharge, the sequence of the sodium polysulfide produced
is Na₂S₅, Na₂S₄, and Na₂S₃.
[0031] The above reaction producing sodium polysulfide is strongly exothermic, generating
heat as it occurs. The region of the second chamber 26 immediately adjacent to the
outer surface 30, as well as the outer surface 30 itself, are preferentially heated
above the general operating temperature at which the cell 10 as a whole is maintained.
The heat diffuses away from the point of production over time. However, if the discharge
of the cell is rapid, the heat does not have time to diffuse away, and there is a
heat buildup. The heat buildup is particularly acute when the cell 10 is operated
in a weightless environment, because there are no natural gravity driven convection
currents in the sulfur to accelerate heat transfer. Figure 3 is a pictorial representation
of the same region as Figure 2, showing on the superimposed graph the temperature
as a function of position along the cylindrical radius of the cell 10.
[0032] When the cell 10 is charged, the reverse reactions occur.
[0033] The sodium is the anode of the cell defined by this reaction, and is externally connected
to an external circuit 32 through a negative electrode 34 in the top portion 14 of
the housing 12 of the cell 10. The sulfur is the cathode of the cell defined by this
reaction, and is externally connected to the external circuit 32 through a positive
electrode 36 in the bottom portion 16 of the housing 12 of the cell 10. The graphite
fibers in the felt 28 help to carry the electrical current from the point of the electrochemical
reaction, near the outer surface 30 of the electrolyte, through the second chamber
26 to the housing 12 and thence to the positive electrode 36. No such aid is required
to conduct electrical current through the molten sodium, where current is carried
by metallic conduction.
[0034] Again referring to Figure 3, bubbles of gaseous sulfur 38 may be formed in the sulfur
within the second chamber 26 during operation of the cell 10. If the cell 10 were
operated in a terrestrial environment under the influence of gravity, the bubbles
38 would float upwardly because of their lower density than the sulfur, and would
be harmlessly dissipated at the top of the second chamber 26. In a weightless environment,
however, the bubbles 38 do not float, and instead would remain motionless in the sulfur
unless driven to move by some other force.
[0035] Such a driving force for movement of the bubbles 38 is present in the form of the
temperature gradient producing an increased temperature in the portion of the second
chamber 26 adjacent to the outer surface 30 of the electrolyte 22. In a weightless
environment, it has been observed in other contexts that bubbles of gas in a fluid
tend to migrate toward the highest temperature portion of the fluid, a phenomenon
known as the Maringoni effect. The same principle drives the bubbles 38 toward the
outer surface 30. Over time and as depicted in Figure 3, the bubbles 38 accumulate
adjacent to the outer surface 30 of the electrolyte 22, forming a boundary layer of
bubbles that impede the movement of sulfur toward, and reaction products away from,
the outer surface 30. The cell reaction is therefore impeded, and the apparent cell
electrical impedance increases over time.
[0036] In its preferred form, the present invention prevents the formation of bubbles in
the sulfur entirely, so that there are no bubbles present in the sulfur to migrate
toward the surface 30. Bubble formation is suppressed by applying a positive pressure
to the surface of the sulfur cathode. The positive pressure must be sufficiently high
to prevent vaporization of the sulfur. At the preferred operating temperature of 350
C, the vapor pressure of sulfur is about 1/2 atmosphere. At least about 1/2 atmosphere
of positive pressure must therefore be applied to the surface of the sulfur to prevent
vaporization.
[0037] The positive pressure may be applied in several ways. The favored approach is to
apply a gas pressure to a surface of the sulfur cathode within the second chamber
26. The selected gas should be substantially insoluble in the sulfur, as otherwise
it would only further contribute to the potential problem by itself entering the sulfur
and possibly forming bubbles. As used herein, "substantially insoluble" means that
the gas preferably has no solubility in the sulfur, but it is recognized that virtually
all gases will have at least some very small solubility in molten sulfur. Such very
small solubility is acceptable in operation of the invention.
[0038] The most preferred procedure for providing a positive gas pressure is to include
within the chamber a sufficient amount of a compound 40 that decomposes at the operating
temperature of the cell 10 to produce a gas that is substantially insoluble in the
sulfur. The decomposition of the compound should not produce any other products that
would interfere with the operation of the cell, as by contamination of the sulfur.
The compound 40 must be provided at a point remote from the portion of the second
chamber 26 adjacent to the outer surface 30, so that the product pressurizing gas
cannot find its way to the region adjacent to the outer surface 30, as again this
would contribute to the potential problem.
[0039] The most preferred compound for providing the pressurizing gas is sodium azide, NaN₃.
Sodium azide decomposes at the cell operating temperature to produce sodium and diatomic
nitrogen gas, which is substantially insoluble in liquid sulfur. The sodium is not
a contaminant, as sodium naturally enters the sulfur during the discharge reaction
described above. The solid sodium azide is initially positioned at one end of the
second chamber 26 remote from the electrolyte 22 and separated from the sulfur by
a carbon separator 41, see Figure 1. When the cell 10 is heated to its operating temperature,
the sodium azide decomposes, producing a nitrogen pressurizing gas that prevents formation
of bubbles in the sulfur. The pressure of the gas is determined by the amount of sodium
azide initially furnished and vaporized.
[0040] Some further details of the construction of the most preferred form of the cell 10
are provided for illustrative purposes, but are not to be taken as limiting of the
invention, as the invention may equally well be applied to other forms of the cell.
The overall length of the cell 10 is about 254 mm (10 inches), and the outer diameter
of the housing 12 is about 35 mm (1-3/8 inches). The housing 12 is formed of chromium
coated stainless steel or molybdenum, which is resistant to corrosion by the sulfur,
about 0,51 mm (0.020 inches) thick. The protection tube 20 is formed of stainless
steel, about 10,38 mm (0.015 inches) thick. The electrolyte is the previously described
ceramic material about 1,14 mm (0.045 inches) thick. The first chamber 24, the space
between the outer diameter of the protection tube 20 and the inner diameter of the
electrolyte 22, is about 0,51 mm (0.020 inches) wide. The second chamber 26, the space
between the outer diameter of the electrolyte 22 and the inner diameter of the housing
12, is about 4,32 mm (0.170 inches)wide. To attain a pressurising pressure of about
2 atmospheres at the cell operating temperature of 350 C, about 2-5 grams of sodium
azide is furnished.
[0041] The cell 10 of the invention produces an open circuit voltage of about 2.08 volts
over most of its capacity range. The cell having the preferred dimensions and characteristics
just described has a capacity of about 40 ampere-hours. In normal spacecraft construction,
a number of the individual cells are connected together in an appropriate fashion
to provide power of the required voltage and capacity.
[0042] Another approach to pressurizing the sulfur to prevent the formation of bubbles is
illustrated in Figure 4. A pressurizing gas such as nitrogen is applied from an external
source 50 to the surface of the sulfur remote from the outer surface 30 of the electrolyte,
through a gas delivery tube 52. This approach has the advantages that the pressure
could be maintained constant regardless of the level of liquid in the second chamber
26, and that the gas pressure in all of the cells that form a battery could be controlled
during operation by a single valve 54. It has the disadvantage that the individual
cells would no longer be sealed, so that a single leak anywhere in the system could
cause failure of the entire battery. For this reason, the approach of using a compound
40 inside a sealed cell is preferred. Failure of one cell will not propagate to cause
failure of the entire battery.
[0043] By applying a sufficiently great pressure to the sulfur by any acceptable method,
formation of bubbles in the sulfur is suppressed. As a result, there are no bubbles
present in the sulfur that might migrate in the manner illustrated in Figure 3 to
interfere with operation of the cell in a weightless environment. Removal of previously
formed bubbles is an alternative approach, but is not preferred because of the difficulty
of removing bubbles from the felt-filled second chamber 26. Instead, it is preferred
to prevent formation of any bubbles.
[0044] The cell 10 of the invention is operable in a weightless environment without degradation
of performance by formation of bubbles formed in the sulfur. Formation of bubbles
in the sodium is not a problem, because of its much higher boiling point.